Low gassing zinc dust paint



Jan. 17, 1961 w. J. LANTZ 2,968,571

LOW GASSING ZINC DUST PAINT Filed Aug. 13, 1959 HHTE 0F 6H8 FOR/"IHT/ON lN ZINC DUST PRINT 5% TETRHET/IYL ORTHOS/LICHTE ON THE OIL HCCELERHTED WITH D/'THYLENE TR/HMINE TIME IN DFIY5 5% T606 0N OIL TIME IN HOURS TIME IN HOURS INVENTOR BYfw/Mm ATTORNEYS LOW GASSIN G ZINC DUST PAINT Willard J. Lantz, Nixon, N.J., assignor to American Smelting and Refining Company, New York, N.Y., a corporation of New Jersey Filed Aug. 13, 1959, Ser. No. 833,640

Claims. (Cl. 106-14) This invention relates in general to zinc dust paints and more particularly to an improved zinc dust paint having relatively low gassing properties.

Zinc dust paints are commonly of four types, (1) V paints containing zinc dust extended with other pigments such as zinc oxide, (2) zinc-rich paints containing up to 93 to 95 percent by weight of zinc in the dry organic film, (3) the heat resistant zinodust paints and (4) the inorganic silicate type vehicle paints. The heat resistant type paints are the petroleum resin paints, butyl titanate and silicone resin paints. The inorganic silicate vehicle paints are sodium silicate containing zinc dust paints. The zinc-rich paint vehicles are generally those which dry from solvent evaporation, such as chlorinated rubber, polystyrene, polyvinyl chloride-acetate copolymers and the like.

In the extended or conventional zinc dust paints, linseed oil and oleoresinous vehicles are customarily employed. The extender pigment is preferably zinc oxide and other pigments may be employed to achieve any desired color in the paint. Customarily the ratio of zinc dust to the zinc oxide extender is maintained at approximately four to one and the total pigment content of the dry film may be about 80 percent by weight.

Gas evolution from such formulations in packaged storage containers has been the greatest problem with zinc paints and has resulted in a poor market because of storage and packaging problems. Many manufacturers use rubber gaskets to allow for inevitable gas leakage while others provide two-compartment containers wherein the zinc dust is separately packaged. It has been suggested that the presence of moisture is the primary cause of gas evolution on prolonged storage of zinc paints together with a secondary possibility of gas formation on direct reaction between the zinc and the free fatty acid or acid content of the paint vehicle. These reactions may take the following course with accompanying evolution of hydrogen and development of excessive pressure in the container:

Heretofore attempts made at inhibiting gas evolution in zinc containing paints involved the use of hygroscopic materials, particularly calcium oxide, silca gel and the like, the purpose of which is to absorb or chemically immobilize the moisture which is either present in the paints initially or formed in the above described manner. None of these materials have proved satisfactory. The silica gel, while effective to a degree, causes an objectionable increase in the viscosity of the paint.

It has been found that gas evolution in paint compositions may be effectively controlled by the incorporation of an additive comprising tetraethyl orthosilicate into the zinc paint formulation. It has also been found that the tates Patent:

effectiveness of the additive may be significantly increased if the acid number of the vehicle is maintained at a low value but above complete neutrality. Accordingly, it is found that gas evolution is reduced to an absolute minimum by incorporation of tetraethyl orthosilicate as an additive to the vehicle together with a suflicient amount of diethylene triamine or other basic material to approximately that required, or preferably slightly less than that required, to. neutralize the acid content of the paint vehicle. Where the vehicle is a glyceride drying oil, it is found that the addition of diethylene triamine in amount just less than that theoretically required to neutralize the free fatty acid in the oil remarkably accelerates the reaction of the tetraethyl orthosilicate with the moisture in the vehicle. The reaction of the tetraethyl orthosilicate with the aqueous content of the zinc paint results in the formation of ethanol and silica in accordance with the following reaction:

The reaction occurs only under controlled conditions. In accordance with the present invention, it has been found that optimum results are obtained by adding the active reagent to the paint drying oil approximately twenty-four hours prior to paint manufacture. The amount of the tetraethyl orthosilicate may vary widely, and even minute amounts tend to retard the gassing tendency. In many instances successful results are achieved by the addition of from 4 to 6 percent, preferably around 5 percent, of the tetraethyl orthosilicate based upon the weight of the drying oil. It is observed that the zinc oxide extender originally contains the greatest quantity of moisture although the moisture inherently contained in the linseed oil is the more reactive.

PREPARATION OF PAINT A conventional type zinc dust paint is prepared by ball milling zinc oxide and the treated oil or oleoresinous vehicle in the approximate ratio of 1:1 for approximately twenty-four hours to produce the paint base. After this period, the remaining oil thinners and driers are incorporated along with the zinc dust pigment. The resulting formulation has approximately the following composition:

62.4 parts zinc dust 15.6 parts zinc oxide 20.6 parts treated raw linseed oil 1.4 parts thinners and driers GAS TESTS ON ZINC DUST/ZINC OXIDE PAINTS The antigassingeffect of tetraethyl orthosilicate was determined by two methods (1) the can test method and (2) the straight tube manometer method. The can test consists of placing two ounces of the test sample of paint in a 2% ounce can sealed with epoxy cement. The test cans are placed in a clamping frame in an oven at F. and allowed to remain for a given period of time. On removal, the cans are allowed to come to room temperature and are tested by puncturing with a dial-type gage. The pressure is recorded in pounds per square inch. The antigassing effect of tetraethyl orthosilicate was compared with the antigassing effect of triisopropyl borate and aluminum isopropylate materials which should react in a similar manner.

A second test method using a straight tube manometer was employed wherein about 100 milliliters of the test paint is poured into a glass tube. The tube is placed in a water bath at 125 F. and the straight tube manometer It is, accordingly, feasible by virtue of the present invention to provide packaged .zinc dust paint with virtually unlimited shelf life capacity;

Figs. 2 and 3 show the rate of water reaction in oils is inserted and fastened. After the paint has reached the 5 containing 5 and 8 percent tetraethyl orthosilicate. rebath temperature, the system is then sealed and the presspectively. In these experiments using the Karl Fischer sure developed by the paint is read in millimeters of reagent, the rate of water reaction with the silicate in the mercury corrected for barometric variations. vehicle was measured in oils containing approximately 5 The results of these tests are set forth in the followand 8 percent tetraethyl orthosilicate based on the oil. ing tables: 10 As shown in these figures, the addition of diethylene tri- T able 1 Pressure Duration 7 Additive Amount How Added (mm. of of Test Remarks Hg) in Days Trilsopropyl bor 170 as Do 132 33 112 33 92 33 57,67 53 42 52 1.50%... -.do 26 52 0.25% on dust.-. with zinc dust 269.253 66 do as solution with zinc 350.330 7 Additive caused dust. paint to gel. 0.5% on dust-.- with dust 23,35 95 As shown by these results the tetraethyl orthosilicate amine has a remarkable effect on the reaction rate of the was remarkably superior in antigassing eifect on zinc tetraethyl orthosilicate with the moisture content of paint to the prior known additives. 30 the oil.

In a further series of accelerated aging tests at 125 F. The above experiments demonstrate the effectiveness the antigassing effect of tetraethyl orthosilicate (TEOS) of tetraethyl orthosilicate as a gas inhibitor for drying oil alone and in the presence of lime (CaO) and diethylene type paints both in the presence and absence of a neutriamine (DTA) was measured with the following results: tralizing reagent. As basic formulations for linseed oil,

T bl H 5 alkyd resin and phenolic resin paints, mixtures of Federal a e Specification TT-P-64lb primer, paint, zinc dust-zinc oxide for galvanized surfaces have been used. Federal Additive Amount How Added specifications require that all three types of paint be pack- Hg.) in Days aged In two compartment cans separating the zinc dust from the paint base. Some paint manufacturers have None 430 3 produced oil and alkyd zinc dust paint formulations as 8* dust" 11 one packaged item, but there is no case known where a0 do do 234,203 20 DTA 0.13% on paint to paint base 103 9 phenolic type zinc dust-zinc oxide paints are packaged 3S9. CaO 0.05% on dust-- 29 32 45 ready for 1186- 5 g-g,.,. STABILIZATION 0F PHENOLIC RESIN a rm 2?. 32 TEOS 5 ZINC PAINTS 20 32 A phenolic resin zinc dust paint is prepared from a 15 32 phenolic resin vehicle consisting of the reaction product 21 17 of a phenol formaldehyde resin with selected drying oils. A paraphenylphenol formaldehyde resin is cooked with 11 17 equal parts of tung and linseed oils in the ratio of 100 0 17 pounds of resin to 25 gallons of vegetable oil. The vis- 4 17 cosity of the product is controlled by the addition of sol- TEOSW; 1j75% do 13,17 55 vents so that the resin varnish resulting contained about 1 Cap to paint and dust 25.25 65 percent solids. The acid number of the phenolic git 53%: is paint 6,6 55 varnish is determined by well-known titration procedures. neutralize acid- A Zinc dust phenolic resin paint can be then formulated having the following composition:

1 This test was made at 100 F. instead of the usual 125 F. in order to 60 obtain some value for comparison. Tests run at 125 F. exceed 450 mm. Z1116 dust Hginuhwrs- 12.8% zinc oxide Referring to the appended drawings: 183% phFnollc varmsl} vehlcle Fig. 1 shows the gas formation measured in millimeters 179% thmners and duets mercury during a y f p As Shown in Gas tests performed on this paint formulation congas at a mlnuflun} even at the e11d of sisted in the addition of varying quantities of tetraethyl the 100 y test P? At thls time, gas formatlon orthosilicate with diethylene triamine to the phenolic paint aIIlOuntefi y sllghtly more than. one f f P with a resulting decrease in gassing tendency. sure while the average pressure considered critical in the The use f the accepted standard amount of usual l. Packagmg of a Palms 15 111 the pelshborhood of cium oxide transformed the phenolic paint into a gel about eight pounds. Of remarkable slgnlficance, howwhich was incapable f testing ever, is the fact that maximum gas formation occurs during the initial 14 day period. Since after packaging the STABILIZATION 0F gi RESIN C U paint would normally remain under the control of the INTS I manufacturer, it is possible to release gas pressure before The stabilizing action of tetraethyl orthosilicate on the paint is in the market. alkyd resin *zinc dust paints was determined by preparing a base formulation having approximately the following composition:

The alkyd resin vehicle used in the formulation was a Beckosol P38l-70 consisting of a solution of alkyd resin in organic solvents to the amount of 70 percent solids. In preparing the paint, a base is prepared by grinding approximately 90 grams of zinc oxide extender with 30 grams of the alkyd resin solution in the presence of 1.5 grams of tetraethyl orthosilicate, 0.15 cc. diethylene triamine and 28.5 grams of mineral spirits. The balance of the paint ingredients are thoroughly mixed with the base formulation to form the alkyd resin paint. The modified alkyd resin paint is then subjected to gassing experiments, the results of which are set forth in the following tables:

CAN TESTS ON ZINC DUST/ZINC OXIDE AYLKD PAINT Test Conditions: 7 days at 125 F. Additive: Tetraethyl orthosilicate added to finished paint. No diethylene triamine used.

Amount of Additive on Wt. Basis of Paint Pressure in Table IV STRAIGHT TUBE MANOMETER TESTS ON ZINC DUST/ ZINC OXIDE ALKYD PAINT Test Temperature: 125 F.

Additive: Tetraethy] orthosilicate added on basis of alkyd resin solution and diethylene triamine added on basis of acid numbers of alkyd resin solid.

These experiments clearly illustrate the antigassing properties of tetraethyl orthosilicate on alkyd resin type zinc dust paints. in all cases. irrespective of the paint vehicle, the tetraethyl orthosilicate functions actively to immobilize the gassing tendency of aqueous components of the paint mixture in the presence of zinc and zinc oxide without objectionable side eliects on the other paint components, which have characterized the prior art ingredients. The use of calcium oxide must be limited to small quantities since larger amounts alter the performance characteristics of the paint producing porous and bleached out surface films. Tetraethyl orthosilicate may be used in relatively large amounts without deleteriously affecting the paint. stantially evaporated.

It will be appreciated that the claimed ingredient functions efiectively to reduce gassing tendencies in zinc type paints, irrespective of the characteristics of the paint vehicle and other ingredients commonly employed in such paint formulations. Various changes and alterations may be made in such formulations without departing from the scope of the invention as defined by the appended claims.

What I claim is:

1. A paint composition comprising zinc dust, a vehicle selected from the class consisting of vegetable drying oil paints, phenolic resin paints and alkyd resin paints, tetraethyl orthosilicate in an amount of from about 1.25 to 8.0 percent based on the vehicle and a neutralizer in an amount of substantially reduce the acid number of the vehicle.

2. A paint composition as set forth in claim 1, wherein the vehicle is a vegetable drying oil paint.

3. A paint composition as set forth in claim 1 in which the vehicle is a phenolic resin paint.

4. A paint composition as set forth in claim 1 in which the vehicle is an alkyd resin paint.

5. A paint composition as set forth in claim 1 in which the neutralizer is present in an amount to reduce the acid number of the vehicle to just above neutrality.

6. A paint composition comprising zinc dust, a vegetable drying oil vehicle, tetraethyl orthosilicate in an amount of from about 1.25 to 8.0 percent based on the vehicle and a neutralizer in an amount to reduce the acid number of the vehicle to just above neutrality.

7. A paint composition as set forth in claim 6 in which the tetraethyl orthosilicate is present in an amount of from about 4 to 6 percent based on the vehicle.

8. A paint composition as set forth in claim 6, wherein the tetraethyl orthosilicate is present in an amount of about 5 percent based on the vehicle.

9. A paint composition comprising zinc dust, a vegetable drying oil vehicle, tetraethyl orthosilicate in an amount of from about 1.25 to 8.0 percent based on the vehicle and diethylene triamine in an amount to reduce the acid number of the vehicle to just above neutrality.

10. A paint composition comprising zinc dust, a vehicle selected from the class consisting of vegetable drying oil paints, phenolic resin paints and alkyd resin paints, tetraethyl orthosilicate in an amount of from about 4 to 6 percent based on the vehicle and diethylene triamine in an amount to reduce the acid number of the vehicle to just above neutrality.

While drying, the material is sub- References Cited in the file of this patent UNITED STATES PATENTS 1,927,117 Friedrich Sept. 19, 1933 2,044,292 Grady June 16, 1936 2,450,327 Cogan Sept. 28, 1948 2,524,357 Robey Oct. 3, 1950 2,540,108 Fisher ]Feb. 6, 1951 2,585,609 Wills Feb. 12, 1952 2,870,035 Allen Ian. 20, 1959 2,882,177 Newton Apr. 14, 1959 2,913,419 Alexander Nov. 17, 1959 UNITED STATES PATENT oTTTcE CETFICAHFT F QGHJREQlN Patenlr, No 2368 571 January l7 1961 Willard J0 Lantlz It is hereby certified that error appears in the above numbered pat ent requiring correction and chat the said Letters Patent should read as corrected below.

Column 5 line 22, before "CAN TESTS ON ZINC DUSTYZINC OXIDE AYLKD PAINT insert the heading Table III --=g column 6 line l6 for "amount of read amount to a Signed and sealed this 6th day of June 19610 (SEAL) Attest:

ERNEST W SWIDERv DAVID L. LADD Attesting Officer Commissioner of Patents 

1. A PAINT COMPOSITION COMPRISING ZINC DUST, A VEHICLE SELECTED FROM THE CLASS CONSISTING OF VEGETABLE DRYING OIL PAINTS, PHENOLIC RESIN PAINTS AND ALKYD RESIN PAINTS, TETRAETHYL ORTHOSILICATE IN AN AMOUNT OF FROM ABOUT 1.25 TO 8.0 PERCENT BASED ON THE VEHICLE AND A NEUTRALIZER IN AN AMOUNT OF SUBSTANTIALLY REDUCE THE ACID NUMBER OF THE VEHICLE. 